559 Index a C–C bond formation reactions 301, 302 acidic substrates deprotonation chalcogenide clusters 97–99 – f-element–metal complexes 60 chromium 139–141 – oligomerization 60, 61 cluster compounds adduct formation – classes 485 – Coulomb attraction, ionic species 57 –Zintlcompounds,see Zintl compounds – and ligand rearrangement, Fe/Yb system 59 cobalt – [MCp*] (M = Al, Ga) and f-element moieties 58 – Co(I) and Co(II) oxidation 279 –RE–Snbonds 59 – Co–Co bond length 279 alkane and amine elimination – dicobalt compounds, see dicobalt compounds – CH-activation, coligand periphery 54 – doublet and quartet spin states 284 –[Cp3USnPh3]preparation 53 – extended metal-atom chains (EMACs) 282 – homogeneous reaction behaviour 51 – Hückel molecular orbital method 284 –RE–Rebonds 53 – intermolecular interactions 283 –U–Rebonds 54 – LUMO 284 alkane elimination 466 – polymorphism 283 allylic and benzylic oxidations 301 – tri- and penta-nuclear cobalt 284 amido, imido and nitride complexes 92, 93, 95 complete active space self consistent field (CASSCF) 2 b complexes BIAN, see 1,2-diiminoacenaphthenes (BIAN) – with actinide metals 69 bimetallic compounds – with rare earth metals 66 – dinickel compounds, see dinickel compounds conductive atomic force microscopy (CAFM) 13 – dipalladium, see dipalladium compounds copper(I)–copper(I) interactions – diplatinum, see diplatinum compounds – ab initio investigation 399 – heterobimetallic, see heterobimetallic compounds – acetonitrile and cuprophilic interaction 401 – metal–metal bonds 325 – carbanion-bridged systems 400 borylene bridging dimanganese(I) complexes 178, – copper–copper bond order 402 179 – Cu–Cu distances 398 bridging/terminal Pn atoms – cyclic trimer 402 – cationic complexes 548 – dicopper complexes 401 – 92 and 94 core structures 548, 549 – gold(I)–gold(I) interactions, see gold(I)–gold(I) interactions c – Hückel calculations 398 CAFM, see conductive atomic force microscopy – hydride bridges 400 (CAFM) – hydrogen bonding 403 carbene bridging dimanganese(I) complexes 178 – linear geometry 401 carboxylate 250, 252 – lithium 402 CASSCF, see complete active space self consistent field – metal–metal bonding 400 (CASSCF) – silver(I)–silver(I) interactions, see silver(I)–silver(I) catecholates 248, 249 interactions Molecular Metal-Metal Bonds: Compounds, Synthesis, Properties, First Edition. Edited by Stephen T. Liddle. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2015 by Wiley-VCH Verlag GmbH & Co. KGaA. 560 Index copper(I)–copper(I) interactions (contd.) – arenes 330 – tetrameric (trimethylsilyl)methyl copper 398 – with aryl and aryne ligands 335–337 – triazenido ligands 398 – bis(phosphane) ligands 338 covalent metal–metal bonding – bisdentate monoanionic carboxylates 328 – Figgis/Martin scheme 415 – bridging ligands 330 – gold–gold bonding, see gold–gold bonding – H-migration mechanism 332 – mixed-valent copper(I)/copper(II) complexes 415, – LiN(SiMe3)2 338 417 – mechanism 330, 331 – paddlewheel complexes of copper(II) 415 – mediated hydrodesulfurization 338, 339 – silver–silver bonding 418, 419 – molecular hinge, Ni(I)–Ni(I) bond 332, 334 cyclo-organobismuthines 524 – monoanionic pyrrole-based PNP pincer cyclo-organostibines ligand 340 – dehalogenation, organoantimony dihalides 523 – monoatomic bridged Ni(I)–Ni(I) bond 338 – description 523 – μ-iodide μ-nitrosyl compound 339 – molecular and supramolecular structure 524, 525 – multidentate N,P-donor ligands 339 – solid state structure 523 – N-heterocyclic carbene (NHC) ligand 338 – supramolecular structure 524 – Ni(I)–Ni(I) bond lengths 329 – N,N ′-trimethylsilyl-phenylamidinate ligand 328 d – salt elimination 332 DAD, see 1,4-diazadienes (DAD) ligands – stepwise reduction, Ni(II) dibromide 335, 336 d-block-group 13 464 – syn-η2:η2-bonding model 330, 332 – alkane elimination 466 dinickel(II) compounds – anionic gallium analogues 465 – carbene ligand (RR′C2−) 344 – diyl systems 465 –closed-shelld8 electronic configuration 340 – metal-mediated dehydrogenation 465 – imide (AdN2−) bridging 342 – organometallic complexes 465 – μ-methylene compound 344 – oxidative addition vs. adduct formation 466, 467 – μ-Nimide bridging compounds 342 – salt elimination 465, 466 – Ni(II)–Ni(II) bond lengths 342, 344 density functional theory (DFT) 3 – paddlewheel 341 1,4-diazadienes (DAD) ligands 51 dinickel(III) compounds 344, 345 dicobalt compounds 279 dipalladium compounds – antiferromagnetic interactions 281 – description 347 – dicobalt paddlewheel compounds 280 – dipalladium, see dipalladium(0) compounds – magnetic communication 282 – dipalladium(I), see dipalladium(I) compounds – N-donor bridging ligands 280 – dipalladium(II), see dipalladium(II) compounds – one-electron oxidation 281 – dipalladium(III), see dipalladium(III) compounds – tetragonal species 280 – mixed-valent 370 1,2-diiminoacenaphthenes (BIAN) 51, 52 dipalladium(0) compounds diiron – aluminium(I) ligand 348 – Fe–Fe bonding 233, 235, 236 – μ-P, P′-coordinated diphosphane ligands 348 – planar paddlewheel complex 231 – Pd(0)–Pd(0) bond lengths 348 – tetragonal complexes 226, 227 – steric bulky Ga(I) ligand [GaCp∗Ph] 347 – trigonal paddlewheel complexes 228–231 dipalladium(I) compounds dimeric magnesium(I) compounds 30, 31 – allyl bridging and insertion of CO2 360, 361 dinickel compounds 326 – bis-NHC ligand 362 – dinickel(0), see dinickel(0) compounds – chiral ligand 358 – dinickel(I), see dinickel(I) compounds – ‘corner- and edge-sharing’ 349, 350 – dinickel(II), see dinickel(II) compounds – gallium(III) halide 358 – dinickel(III) 344, 345 – with mono-bridging-atom ligand 354 – mixed-valent 345, 346 – neutral arene, anionic allyl/cyclopentadiene ligands dinickel(0) compounds 358 – Ni(0)–Ni(0) bond lengths 326, 327 – NPN-tridentate ligands 360 – olefin ligands 326 – paddlewheel compounds, see paddlewheel dinickel(I) compounds compounds – α-diimine 335 – Pd(I)–Pd(I) bond lengths 351, 362 – anionic NHC ligand 339 – Pd-phenyl interactions 358 – antiferromagnetic coupling 329 – pyrrole-based PNP pincer ligand 361 Index 561 – redox non-innocent ligands 362 – description 379 – triene-bridging dipalladium(I) sandwich compounds – ortho-C–H bond of phenol 380 359, 360 – paddlewheel 382, 383 – with unsupported Pd(I)–Pd(I) bond 349, 350, 352, – Pt(III)–Pt(III) bond lengths 381 353 – Pt(III)–Pt(III) compounds 198 and 199 380 dipalladium(II) compounds – Pt(IV) trimethyl compound, C6 D6 solution 380, – with 2-arylpyridine ligand 363, 364 381 – benzylidenic C=C double bond 364 dirhodium complexes – bis(pentalene) compound 144 364, 366 – carboxylate-containing residues 305 – catalytic functionalization, C–H bond 363 – catalytic cycle 303 8 – d electron configuration 363 – excited-state photophysical properties 304 – paddlewheel compounds 364, 365 – as hosts 305, 306 – Pd(II)–Pd(II) bis-(monoanionic-allyl) compound – multielectron transfer reactions 303 366 – multimetallic assemblies 310, 312, 314 dipalladium(III) compounds – π-arene interactions 306, 307 – catalytic C–H bond acetoxylation 367, 368 – π-backbonding 308, 309 – C–Cl bond 367 diruthenium – 146 147 compunds 366 – metal–metal bonds 237 – 155-156 compounds 368 – paddlewheel, see paddlewheels – as intermediate for Pd(II)/Pd(IV) oxidation. 367, distibines and dibismuthines 519 369 – examples of reactions 520, 521 – Pd(III)–Pd(III) bond lengths 367 – Pn–Pn bond formation 520 – UV–vis spectroscopy 367, 369 – secondary 520 diplatinum compounds – structures 520, 522 – description 370 dorbitals – diplatinum(0), see diplatinum(0) compounds – bends and stretches, Ru (dpa) X and Cr (dpa) X – diplatinum(I), see diplatinum(I) compounds 3 4 2 3 4 2 12, 13 – diplatinum(II), see diplatinum(II) compounds – dirhodium carbene complex Rh (HCOO) (CH ) – diplatinum(III), see diplatinum(III) compounds 2 4 2 10, 11, 12 – metal–metal bonded moieties 371 – electron–electron repulsions 7 – mixed-valent 382–384 –Fe(CO) 15, 16 diplatinum(0) compounds 2 9 – iconic quadruple bond [Re Cl ]2− 7, 8 – 160-163 compounds 371 2 8 – naked transition metal diatomics 6 – kinetical stabilisation 371 3− – Pt(0)–Pt(0) bond lengths 372 –[Ru2Cl9] ,M2X9 family 14 σ – series of 371, 372 – bonding 9 diplatinum(I) compounds 371 – singlet ground state, sextuply bonded W2 6 – spherically symmetric 3d cores 7 –BrønstedacidCF3 SO3 H 372, 373 – comproportionation reaction 374 – ‘supported’ and ‘unsupported’ bonds 5 –C(sp1)–P bond 372, 374 – ultrashort Cr–Cr quintuple bonds 9, 10 – diphosphane bridging 375 double-bonded species – diplatinum(I) hydride 376 – dipnictenes structure 530 – E–H bond activated products 376 – selected structural data 530, 531 – phosphide bridged, bis-ethylene compound 166 – 33 structure 529 371, 372 – 35 structure 530, 532 − – 34-Tbt and [34-Bbt]•− structure 530, 531 – phosphinito (R2PO ) bridging 374 – Pt(I)–Pt(I) bond lengths 373 double bonds (E=E) diplatinum(II) compounds – cyclic silylenes 496 – 194 compound 376, 379 – description 494 – description 376 – distannanes bonding 38, 494, 495 – hydride- and acetylide-bridging compounds 376, – refined bonding model 495 378 – sila-butadienes 496 – hydride bridged Pt(II)–Pt(II) bond 379 – Si=Si and Ge=Ge bonds reactivity 497 – macrocyclic N2 S2 ligand 376, 378 – trans-bent structure, 38 [R=CH(SiMe3)2] 494 t – Pt(II)–Pt(II) bond lengths 378 – trialkylsilyl derivative [( BuMe2Si)2Sn]2 495 diplatinum(III) compounds double bonds (Tm=E) 508, 509 – 206 and 207 compounds 381, 382 double salt elimination 468 562 Index e f-element–TM bond formation 48 early-late heterobimetallic complexes – early salt elimination reactions 49